CN1558826A - Laminated film - Google Patents
Laminated film Download PDFInfo
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- CN1558826A CN1558826A CNA028189795A CN02818979A CN1558826A CN 1558826 A CN1558826 A CN 1558826A CN A028189795 A CNA028189795 A CN A028189795A CN 02818979 A CN02818979 A CN 02818979A CN 1558826 A CN1558826 A CN 1558826A
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- Prior art keywords
- laminated film
- film
- propylene
- resin
- ethylene
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/043—HDPE, i.e. high density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/12—Surface bonding means and/or assembly means with cutting, punching, piercing, severing or tearing
- Y10T156/1313—Cutting element simultaneously bonds [e.g., cut seaming]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
A laminated film of a propylene resin layer and an ethylene resin layer is provided, which does not require solvent removal and recovery devices, etc., is low in influences against working environments and a danger of occurrence of fire, and has a high interlaminar adhesive force. That is, the invention relates to a laminated film prepared by melt extrusion laminating, without via an anchor coating agent, an ethylene based resin mainly comprising a linear ethylene/alpha-olefin copolymer having: a density of from 0.870 to 0.910 g/cm<3>; and an MFR of from 1 to 100 g/10 min., the copolymer being obtained by copolymerizing ethylene and an alpha-olefin having from 3 to 20 carbon atoms, on the surface of a propylene based resin film formed from a crystalline propylene based random copolymer resin having a melting peak temperature of not higher than 140 DEG C., as prepared using a metallocene catalyst.
Description
Technical field
The present invention relates to the good laminated film of caking property of propylene resin layer and vinylite interlayer.The surface protection that the caking property that relates to propylene resin layer and vinylite interlayer in more detail is good, can be used for packaging bag, printing paper, photo etc., give water-fast.Oil resistivity, give the laminated film of the printing stack membrane of gloss etc.
Background technology
Polyolefin resin film as the surface protection of package bag, printing paper, give resistance to water and oil resistivity and improve purpose such as lustrous surface and be widely used.
Particularly, film hot-pressing being sticked on the method for carrying out surface protection on the paper that has printed is extensively being implemented.As the employed film of such purpose, use mostly at the laminated film of gloss with the low-melting vinylite of biaxial stretch-formed polypropylene film base material superimposed layer of the excellent optical characteristics of the transparency.
As such laminated film, once proposed to be stacked in laminated film on the biaxial stretch-formed polypropylene film base material (spy opens clear 56-42652 communique with melt extruding resin combination that the mixture of lay-up method with vinyl alkyl ester copolymer and ethylene vinyl acetate copolymer constitute, Te Kaiping 4-2431 communique, Te Kaiping 3-73341 communique) or, only by the heating pressurization, attaching film is made the method for printing laminated product, and this film is at the film (spy opens flat 7-117197 communique) that has cooperated the resin-bonded floor of vinylite with aromatic ring alkene metal derivative compound as the straight chain shape ethylene superimposed layer of catalyst.
When biaxial-stretched polypropylene films base material superimposed layer polyvinyl resin,, film substrate need be carried out oxidation processes and pass through tackifier coating agent lamination polyvinyl resin for interlayer adhesion being made the practical no problem level that.
, for the method for using the tackifier coating agent, there is the drying process that needs solvent, equipment strengthens, the diffusion of the solvent odor that takes place during along with drying makes the operating environment deterioration, and breaking out of fire dangerous big is because of applying or drying capacity is restricted problems such as can not improving process velocity.
In addition, under present present situation, for not using the tackifier coating agent for the film of the resin-bonded layer of biaxial stretch-formed polypropylene mesentery base material superimposed layer, a little less than the interlaminar bonding power of film substrate and resin-bonded layer, after to printing paper hot pressing, entrapped air pockets produces the low part of the transparency between printing paper and film, thus the visibility of loss printing information, outward appearance (shape) variation.In addition, owing to be that film and resin-bonded interlayer can be peeled away simply at oriented polypropylene, thus exist a little less than the lamination adhesion strength, and the problem that can not use as goods.
The invention reside in and provide that the strong allyl resin layer of interlaminar bonding power and the laminated film of ethylene resin layer, this film do not need that solvent is removed, retracting device etc., also little for the danger of the influence of operating environment, breaking out of fire, and do not use the tackifier coating agent.
The content of invention
The present invention in depth studies in order to solve such problem, has obtained following result.
Promptly, provide a kind of laminated film according to the 1st invention of the present invention, it is characterized in that use the manufacturing of aromatic ring alkene metal derivative catalyst, the melting hump temperature is that crystallinity propylene below 140 ℃ and 140 ℃ is on the propylene resin film surface that forms of random copolymer resin, not accompanying that alpha-olefin copolymer that tackifier coating agent ground do not melt extrude lamination ethene and carbon number 3～20 obtains, density is 0.870～0.910g/cm
3, MFR is that 1～100g/10 minute straight chain shape ethylene constitutes as the vinylite of principal component.
In addition, provide a kind of laminated film according to the 2nd invention of the present invention, it is that the crystallinity propylene is a random copolymer resin, to 130 ℃ fusing heat (Δ Hm in the 1st invention
130) for ratio (the Δ Hm of total fusing heat (Δ Hm)
130/ Δ Hm) be more than 0.5 and 0.5.
In addition, provide a kind of laminated film according to the 3rd invention of the present invention, it is that vinylite is a polyethylene mixture in the 1st or the 2nd invention, and it is 0.870～0.910g/cm that this mixture carries out that combined polymerization obtains, density by the alpha-olefin of ethene and carbon number 3～20
3, MFR is that high-pressure process low density polyethylene (LDPE) 1～40 weight % that 1～100g/10 minute straight chain shape ethylene 60～99 weight % and MFR are 1～50g/10 minute constitutes.
In addition, provide a kind of laminated film according to the 4th invention of the present invention, it is in the 1st～the 3rd invention, straight chain shape ethylene, and 80 ℃ the elution amount of measuring by temperature rising elution fractionation (TREF) is 90 weight % and more than the 90 weight % with respect to the copolymer total amount.
In addition, provide a kind of laminated film according to the 5th invention of the present invention, it is in the 1st～the 4th invention, and straight chain shape ethylene is to use aromatic ring alkene metal derivative catalyst to make.
In addition, provide a kind of laminated film, it is characterized in that the stack temperature that melt extrudes of vinylite is 150～300 ℃ in the 1st～the 5th invention according to the 6th invention of the present invention.
In addition, provide a kind of printing laminate according to the 7th invention of the present invention, it is that the vinylite face of any one the described laminated film in the 1st～the 6th invention and printing paper are carried out the thermo-compression bonding formation.
The preferred plan that carries out an invention
Crystalline polypropylene is a random copolymer resin
Crystalline polypropylene is a random copolymer resin, use melting hump temperature (being designated hereinafter simply as Tm) be below 140 ℃ and 140 ℃, preferably 80～140 ℃, particularly preferably be 90～135 ℃.Tm surpasses 140 ℃, when extruding lamination, and with the bad adhesion of the vinylite of lamination, outward appearance (distortion) deterioration of the printing laminated product of thermo-compression bonding on printing paper etc., the adhesion strength of printing laminated product is variation also.
At this, Tm is the value of measuring with differential scanning type calorimeter (DSC).Use Seiko society's system (ヤ イ コ one society's system) differential scanning type calorimeter (DSC), the about 5mg of sample thief after keeping 5 minutes under 200 ℃, is cooled to 40 ℃ with 10 ℃/minute cooling rates.Then, obtain Tm with 10 ℃/minute the programming rate melting heat discharge curve that obtains when being melted that heats up.That is, with the maximum peak temperature of melting heat discharge curve as Tm.
The crystallinity propylene is a random copolymer resin, to 130 ℃ fusing heat (Δ Hm
130) for ratio (the Δ Hm of total fusing heat (Δ Hm)
130/ Δ Hm) be more than 0.5 and 0.5, preferably more than 0.6 and 0.6.Δ Hm
130/ Δ Hm) less than 0.5 when extruding lamination, reduce with the adhesion strength of the vinylite of lamination, or the adhesion strength of printing laminated product reduces.
At this, Δ Hm and Δ Hm
130It is the value of measuring by differential scanning type calorimeter (DSC).Obtain Δ Hm and Δ Hm from above-mentioned melting heat discharge curve
130That is, in this melting heat discharge curve, is connected with straight line between the temperature that the temperature that initial heat absorption is begun and all heat absorptions end, as obtaining the baseline that melts heat.To be equivalent to surround this melting heat discharge curve and baseline part the fusing heat as total fusing heat (Δ Hm), will from low temperature side count to 130 ℃ fusing heat as fusing heat (Δ Hm to 130 ℃
130).
In addition, the crystallinity propylene is the melt flow rate (MFR) (JIS-K6921,230 ℃, 2.16kg loading) of random copolymer resin, preferably 0.1～50g/10 minute, more preferably 0.5～40g/10 minute.If MFR is beyond the above-mentioned scope time, the easy variation of the processability of film.
In addition, the used crystallinity propylene of the present invention is the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number-average molecular weight (Mn) of random copolymer resin, preferably 1.5～4.5, more preferably 1.8～4.0, most preferably 2.0～3.0.When if Mw/Mn surpasses above-mentioned scope, the trend that has interlayer adhesion to reduce, if during not enough above-mentioned scope, the processing film deterioration.
As the method that Mw/Mn is adjusted to prescribed limit, can enumerate and select suitable aromatic ring alkene metal derivative catalyst.
In addition, the mensuration of Mw/Mn is to adopt gel permeation chromatography (GPC) to carry out.Condition determination is as follows.
Device: the ウ オ--system GPC150C of ズ society type
Detector: the system 1A of MIRAN society infrared spectrophotometer (measuring wavelength 3.42 μ m)
Post: clear and electrician society makes the AD806M/S3 root, and (correction of post is carried out eastern Cao and is made monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, each 0.5mg/ml solution of F288) mensuration is with the logarithm value of approximate elution volume of 2 power formulas and molecular weight.In addition, the molecular weight of sample uses polystyrene and polyacrylic viscosity formula to be converted into polypropylene.At this, factor alpha=0.723, the logK=-3.967 of the viscosity formula of polystyrene, polypropylene are α=0.707, logK=-3.616.)
Measure temperature: 140 ℃
Concentration: 20mg/10ml
Injection rate: 0.2ml
Solvent: o-dichlorohenzene
Flow velocity: 1.0ml/ minute
Crystallinity propylene used in the present invention is that random copolymer resin is to use the propylene of aromatic ring alkene metal derivative catalyst manufacturing and the random copolymer of alpha-olefin.As the crystallinity propylene is the propylene of random copolymer resin and the alpha-olefin of random copolymerization, can enumerate the alpha-olefin (still, removing propylene) of carbon number 2～20.Particularly ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-amylene-1,4-methyl-hexene-1,4,4-dimethyl pentene-1 etc. can illustratively be arranged.Alpha-olefin promptly can use a kind also can use more than 2 kinds and 2 kinds.Wherein, the most preferably alpha-olefin of carbon number 2, i.e. ethene.
In addition, narrate in the back about aromatic ring alkene metal derivative catalyst.
The crystallinity propylene is the propylene content of random copolymer resin, preferably 60～99 weight %, more preferably 65～98 weight %, alpha-olefin content, preferably 1～40 weight %, 2～35 weight % more preferably.
At above-mentioned crystallinity propylene is in the random copolymer resin, various additives be can add in the scope of not damaging purpose of the present invention, nucleator, lubricant, anti-caking agent, antioxidant, weather-proof stabilizing agent, antistatic additive, antifoggant, colouring agent, low-molecular weight polymer etc. for example can be added as required.
Vinylite
The vinylite that is used for laminated film of the present invention, with straight chain shape ethylene as principal component.Such straight chain shape ethylene be with the alpha-olefin copolymer of ethene and carbon number 3～20 straight chain shape ethylene.
Alpha-olefin as straight chain shape ethylene is the alpha-olefin of carbon number 3～20.Illustrative particularly have propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-heptene, 4-methyl-amylene-1,4-methyl-hexene-1,4, a 4-dimethyl pentene-1 etc.The preferably alpha-olefin of carbon number 3～12, the alpha-olefin of carbon number 3～8 more preferably.Alpha-olefin promptly can use a kind also can use more than 2 kinds.
The ethylene contents of straight chain shape ethylene, preferably 60～99 weight %, more preferably 65～98 weight %, alpha-olefin content, preferably 1～40 weight %, 2～35 weight % more preferably.
The density of straight chain shape ethylene is 0.870～0.910g/cm
3, 0.875～0.900g/cm preferably
3The not enough 0.870g/cm of density
3The time, insufficient formability, caking capacity be variation also, when thermo-compression bondings such as printing paper, might cause the stretching of laminated film and breaks.Density surpasses 0.910g/cm
3The time, with the bad adhesion of the printing surface of block letter, produce the deformed appearances variation.In addition, density is according to JISK6922, uses MFR to measure the value that single thread is measured with the density gradient column method.
In addition, the MFR of straight chain shape ethylene (JIS-K6922,190 ℃, 2.16kg loading) is 1～100g/10 minute, preferably 5～80g/10 minute.MFR is 100g/10 minute and more than 100g/10 minute, because melt viscosity is low excessively, so film forming is poor, and not enough 1g/10 minute of MFR's, outward appearance (distortion) variation of the printing laminated product of thermo-compression bonding on printing paper etc.
In addition, straight chain shape ethylene is from the adaptive viewpoint of printing lamination, by temperature rising elution fractionation (TempreratureRisingElutionFractionation: be designated hereinafter simply as TREF.) 80 ℃ elution amount measuring, with respect to the copolymer total amount be 90 weight % and more than the 90 weight %, 95 weight % and more than the 95 weight % preferably.
In addition, TREF measures, and is the principle that reaches " macromolecule collection of thesis 2P1C09 (1985) " record according to " JournalofA ppliedPolymerScience, Vol26,4217-4231. (1981) ", is undertaken by following.Polymer is dissolved in back cooling in the post of inert carrier that supplied to filling in the solvent fully, forms thin polymeric layer on the inert carrier surface.Then, under defined terms, heat up, measure amount of polymers continuously, obtain representing the curve of the relation of its elution amount and eluting temperature up to this temperature wash-out.The composition that can see polymer according to the shape of such curve distributes.
Below, explain the mensuration of TREF.Use intersection grading plant (ダ イ ヤ イ ソ ス ト Le メ ソ ト makes CFCT101) as determinator.This intersection grading plant is with temperature rising elution fractionation (TREF) mechanism of differential levels sample of utilizing solution temperature, and be with online online mode connect with molecular sieve with classification the fraction further device of the exclusion chromatography (Size ExclusionChromatography:SEC) of classification again.
At first, in the stainless steel post of filling, inject the o-dichlorobenzene solution (concentration 3mg/ml) of the mensuration sample of 0.4ml as internal diameter 4mm, the length 150mm of the bead of inert carrier.Then, with post with 1 ℃/minute speed from 140 ℃ of temperature that are cooled to 0 ℃, coating sample on inert carrier.With post 0 ℃ down keep 30 minutes after, will be injected into SEC post (clear and electrician makes the SD806MS3 root) with 1ml/ minute flow velocity from the TREF post at the composition 2ml of 0 ℃ temperature dissolving.During carrying out the classification of molecular sieve with SEC, be warmed up to following eluting temperature for the TREF post, kept its temperature about 30 minutes.Measure each elutriated fraction of using SEC with 39 minutes interval.With following temperature stage ground rising eluting temperature.
0，5，10，15，20，25，30，35，40，45，49，52，55，58，61，64，67，70，73，76，79，82，85，88，91，94，97，100，102，120，140℃
With the SEC post by the molecular sieve classification solution, measure and the proportional absorbance of concentration of polymer (wavelength 3.42 μ m detect with the stretching vibration of methylene) with being attached to IR spectrophotometer on the device, obtain the chromatogram of each eluting temperature fraction.Use built-in data processing software, the Chromatogram Baseline of each the eluting temperature fraction that obtained by said determination of drawing is carried out calculation process.The area of each chromatogram of integration calculates the integration elution curve.On this integration elution curve, the elution amount that with eluting temperature is 80 ℃ is as 80 ℃ the elution amount of measuring with temperature rising elution fractionation.
In addition, the weight average molecular weight (Mw) of the used straight chain shape ethylene of the present invention and the ratio (Mw/Mn) of number-average molecular weight (Mn) are 1.5～3.0, preferably 1.6～2.8, more preferably 1.7～2.5.If when Mw/Mn surpasses above-mentioned scope,, be unfavorable because the transparency reduces, if during not enough above-mentioned scope, extruding load and rising, shark dermatoglyph etc. takes place easily, often the flexibility (adaptability) of operation variation.
In addition, the mensuration of Mw/Mn is carried out with gel permeation chromatography (GPC).Condition determination is as follows.
Device: the ウ オ--system GPC150C of ズ society type
Detector: the system 1A of MIRAN society infrared spectrophotometer (measuring wavelength 3.42 μ m)
Post: clear and electrician society makes the AD806M/S3 root, and (correction of post is carried out eastern Cao and is made monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, each 0.5mg/ml solution of F288) mensuration is with the logarithm value of approximate stripping volume of 2 power formulas and molecular weight.In addition, the molecular weight of sample uses polystyrene and poly viscosity formula to be converted into polyethylene.At this, factor alpha=0.723, the logK=-3.967 of the viscosity formula of polystyrene, polyethylene are α=0.733, logK=-3.407.)
Measure temperature: 140 ℃
Concentration: 20mg/10ml
Injection rate: 0.2ml
Solvent: o-dichlorohenzene
Flow velocity: 1.0ml/ minute
For straight chain shape ethylene, in the scope of not damaging purpose of the present invention, can add various additives as required and for example can add nucleator, lubricant, anti-caking agent, antioxidant, weather-proof stabilizing agent, antistatic additive, antifoggant, colouring agent, low-molecular weight polymer etc.
Can make straight chain shape ethylene aptly by using aromatic ring alkene metal derivative catalyst.Narrate in the back for aromatic ring alkene metal derivative catalyst.
In straight chain shape ethylene,, can mix MFR (JIS-K6922,190 ℃, 2.16kg loading) and be 1～50g/10 minute high-pressure process low density polyethylene (LDPE) in order to improve the processability (material emerges in large numbers the width of cloth that resembles, contracts) of extruding lamination and adding man-hour.
The cooperation ratio of this moment, straight chain shape ethylene are 60～99 weight %, preferably 70～97 weight %, 80～95 weight % more preferably.The high-pressure process low density polyethylene (LDPE) is 1～40 weight %, preferably 3～30 weight %, 5～20 weight % more preferably.If during high-pressure process low density polyethylene (LDPE) less than 1 weight %, have easy generation material to emerge in large numbers and resemble, the big processability of the amplitude variation that contracts has the trend of deterioration.On the other hand, when surpassing 40 weight % as if the high-pressure process low density polyethylene (LDPE), morphotropism, the glossiness deterioration of often printing laminated product.
Spendable aromatic ring alkene metal derivative catalyst carried out following explanation when manufacturing crystallinity propylene was random copolymer resin and straight chain shape ethylene.
Can use known aromatic ring alkene metal derivative catalyst, but can enumerate the transistion metal compound and the co-catalyst of periodic table the 4th～6 family of the ligand that contains cyclopentadienyi skeleton, the catalyst that organo-aluminum compound as required and carrier constitute.
At this, in the transistion metal compound of periodic table the 4th～6 family that contains the ligand with cyclopentadienyi skeleton, said this cyclopentadienyi skeleton is meant cyclopentadienyl group, substituted cyclopentadienyl etc.As the substituting group of substituted cyclopentadienyl, can enumerate containing brine alkyl, alkoxyl, aryloxy group, hydrocarbyl silyl, phosphorous alkyl, nitrogenous alkyl or containing at least a kind substituting group in boron hydrocarbyl, silicyl, silicyl substituted alkyl, silicyl substituted aryl, cyano group, cyano group alkyl, cyano-aryl, the halo silicyl etc. of the alkyl that is selected from carbon number 1～20, halogen radical, carbon number 1～20.The substituting group of this substituted cyclopentadienyl also can have more than 2, and in addition, also can mutually combine between substituting group forms ring.Mutually combine on the ring that forms between substituting group and then also can have substituting group.
Alkyl as above-mentioned carbon number 1～20, can enumerate alkyl, cycloalkyl, aryl, aralkyl etc., particularly, can enumerate the alkyl of methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, octyl group, 2-ethylhexyl, decyl etc.; The cycloalkyl of cyclopenta, cyclohexyl etc.; The aryl of phenyl, tolyl etc.; The aralkyl of benzyl, neophyl etc. etc.
As between substituting group, be the substituted cyclopentadienyl when forming ring more than 1 or 2 and 2 of mutually combining between hydrocarbon, replacement fluorenyl, the base (ア ズ レ ニ Le) of the substituting group replacement of the substituted naphthyl that the substituted indenyl that the substituting group that can enumerate indenyl, is waited by the alkyl (alkyl etc.) of carbon number 1～8 replaces, naphthyl, the substituting group that is waited by the alkyl (alkyl etc.) of carbon number 1～8 replace, fluorenyl, the alkyl (alkyl etc.) by carbon number 1～8 etc., pass through the substituting group etc. of substituting group replacement of the alkyl (alkyl etc.) etc. of carbon number 1～8.
For the transistion metal compound of periodic table the 4th～6 family that contains the ligand with cyclopentadienyi skeleton, as this transition metal, preferably zirconium, titanium, hafnium etc. particularly preferably are zirconium, hafnium.This transistion metal compound as the ligand with cyclopentadienyi skeleton, has 1～3 usually, has 2 and 2 in addition when above, also can mutually combine by crosslinking group.In addition, as this crosslinking group, can enumerate alkylidene, alkylidene radical, silicylene, methylene germane base etc.These hydrogen atom also can be used replacements such as alkyl, halogen atom.
In the transistion metal compound of periodic table the 4th～6 family, as the ligand beyond the ligand with cyclopentadienyi skeleton, as representational, can enumerate the alkyl (alkyl, thiazolinyl, aryl, alkaryl, aralkyl, polyene-based (Port リ エ ニ Le) etc.) of hydrogen, halogen radical, carbon number 1～20, the oxygen-containing hydrocarbon base of carbon number 1～20, the nitrogenous alkyl of carbon number 1～20, the phosphorous alkyl of carbon number 1～20 or the hydrocarbyl silyl of carbon number 1～20 etc.
As the non-limiting example of the transistion metal compound of periodic table the 4th～6 family that contains ligand, can enumerate following compound with cyclopentadienyi skeleton.
Two (cyclopentadienyl group) zirconiums of dichloro, two (indenyl) zirconiums of dichloro, two (fluorenyl) zirconiums of dichloro, two (laying a foundation) zirconiums of dichloro, dichloro two (4,5,6, the 7-tetrahydro indenyl) zirconium, dichloro (cyclopentadienyl group) (3,4-dimethyl cyclopentadienyl group) zirconium, dichloro di-2-ethylhexylphosphine oxide (cyclopentadienyl group) zirconium, dichloro methylene (cyclopentadienyl group) (3,4-dimethyl cyclopentadienyl group) zirconium, dichloro isopropylidene (cyclopentadienyl group) (3,4-dimethyl cyclopentadienyl group) zirconium, two chlorethylidenes (cyclopentadienyl group) (3,5-dimethyl pentadiene base) zirconium, dichloro di-2-ethylhexylphosphine oxide (indenyl) zirconium, dichloro ethylenebis (2-methyl indenyl) zirconium, two chlorethylidenes 1, two (4-phenyl indenyl) zirconiums of 2-, two chlorethylidenes (cyclopentadienyl group) (fluorenyl) zirconium, dichloro-dimethyl silicylene (cyclopentadienyl group) (tetramethyl-ring pentadienyl) zirconium, two (indenyl) zirconiums of dichloro-dimethyl silicylene, dichloro-dimethyl silicylene two (4,5,6, the 7-tetrahydroindenyl) zirconium, dichloro-dimethyl silicylene (cyclopentadienyl group) (fluorenyl) zirconium, dichloro-dimethyl silicylene (cyclopentadienyl group) (octahydro fluorenyl) zirconium, two [1-(the 2-methyl-4 of dichloromethyl phenyl silicylene, 5-benzo (indenyl))] zirconium, two [1-(2-methyl-4,5-benzo the indenyl)] zirconiums of dichloro-dimethyl silicylene, two [1-(2-methyl-4H-the lays a foundation)] zirconiums of dichloro-dimethyl silicylene, two [1-(2-methyl-4-(4-chlorphenyl)-4H-the lays a foundation)] zirconiums of dichloro-dimethyl silicylene, two [1-(2-ethyl-4-(4-chlorphenyl)-4H-the lays a foundation)] zirconiums of dichloro-dimethyl silicylene, two [1-(2-ethyl-4-naphthyl-4H-the lays a foundation)] zirconiums of dichloro-dimethyl silicylene, two [1-(2-methyl-4-(4-chlorphenyl)-4H-the lays a foundation)] zirconiums of dichloro diphenyl silicylene, two [1-(2-methyl-4-(phenyl indenyl))] zirconiums of dichloro-dimethyl silicylene, two [1-(2-ethyl-4-(phenyl indenyl))] zirconiums of dichloro-dimethyl silicylene, two [1-(2-ethyl-4-naphthyl-4H-the lays a foundation)] zirconiums of dichloro-dimethyl silicylene, two (indenyl) zirconiums of dichloro-dimethyl methylene germane base, dichloro-dimethyl methylene germane base (cyclopentadienyl group) (fluorenyl) zirconium.
In addition, also can enumerate compound same as described above for other the 4th, 5,6 group transition metal compounds of titanium compound, hafnium compound etc.The transistion metal compound that contains periodic table the 4th～6 family of the ligand with cyclopentadienyi skeleton also can use a kind or use with the mixture more than 2 kinds.
As co-catalyst, to be meant the transistion metal compound of above-mentioned periodic table the 4th～6 family can be effectively as polymerization catalyst or will be by the catalyst activity change the ionic electric charge of state carry out balanced compound.As used in the present invention co-catalyst, can enumerate group of the lanthanides salt, tin oxide of aikyiaiurnirsoxan beta Organoaluminoxy compound, lewis acid, ion exchangeable phyllosilicate, boron compound, lanthanas etc. such as (ア Le モ キ サ ソ) etc.
Spendable as required organo-aluminum compound is with general formula (AlR
4 pX
3-p)
qThe compound of expression.For the present invention, can independent, several mixing or and need not wait to say with the compound that use is represented by this formula.In addition, this uses not only when catalyst preparation, and also can use when prepolymerization or polymerization.In this formula, R
4The alkyl of expression carbon number 1～20, X represents halogen, hydrogen, alkoxyl, amino.P to 1～3, q are 1～2 integers.As R
4, alkyl preferably, in addition, when X is halogen, chlorine preferably; When being the alkoxyl base, the alkoxyl of carbon number 1～8 preferably; When amino, the amino of carbon number 1～8 preferably.Wherein, the hydrogenation aluminum dialkyl of the trialkylaluminium of p=3, q=1 and p=2, q=1 (ジ ア Le キ Le ア Le ミ ニ ウ system ヒ De リ De) preferably.R more preferably
4It is the trialkylaluminium of carbon number 1～8.
As spendable carrier as required, the porous oxides of preferably inorganic or organic compound.Can enumerate SiO particularly
2, Al
2O
3, MgO, ZrO
2, TiO
2, B
2O
3, CaO, ZnO, BaO, ThO
2Deng or these mixture, as SiO
2-Al
2O
3, SiO
2-V
2O
5, SiO
2-TiO
2, SiO
2-MgO, SiO
2-Cr
2O
3Deng.Be to use the ion exchangeable layer silicate that has function vector and co-catalyst function concurrently as more preferred example.
Laminated film
Laminated film of the present invention is to be not accompany on the propylene resin film surface that forms of random copolymer resin that tackifier coating agent ground does not melt extrude lamination with above-mentioned vinylite and the laminated film made by above-mentioned crystallinity propylene.
The forming method of propylene resin film can adopt the method for any known, can enumerate the inflatable method of forming, T mold forming method etc.In addition, the propylene resin film can not stretch, and stretches at single shaft or biaxially oriented yet.
For the propylene resin film, also can carry out known surface treatments such as sided corona treatment, flame treatment, plasma treatment.
In addition, the propylene resin film can be used as single thin film and uses, and also can use at the above-mentioned vinylite of surperficial lamination and at other the plural layer film of resin bed of the face superimposed layer of inboard.
On the surface of aforesaid propylene based resin film, do not accompany the tackifier coating agent and vinylite is melt extruded lamination make laminated film.The temperature that melt extrudes of vinylite is 150～300 ℃, preferably 180～280 ℃.If surpass 300 ℃, worry printing lamination adaptability deterioration, if during 150 ℃ of less thaies, the trend that has adhesion strength to reduce.
Laminated film of the present invention, the thickness of propylene resin film be 1～250 μ m, preferably 3～200 μ m, particularly preferably be 5～150 μ m, vinylite be 1～250 μ m, preferably 5～200 μ m, particularly preferably be 7～100 μ m.
Whether the laminated film that obtains like this and uses the tackifier coating agent irrelevant, shows the practical sufficient interlaminar bonding intensity that.Interlaminar bonding intensity is above, the 80g/15mm and 80g/15mm is above, 130g/15mm and more than the 130g/15mm more preferably preferably of 60g/15mm and 60g/15mm.
On laminated film of the present invention, but lamination is given various functions other layer, for example plastic sheeting, aluminium foil, paper etc. as purpose in the scope of not damaging effect of the present invention.And then, on laminated film of the present invention, as required, also can carry out crosslinked etc. the various processing film of metal evaporation processing, Corona discharge Treatment, printing processing, electron ray and handle.
Laminated film of the present invention can use the vinylite layer on heated sealant film, printing stack membrane etc. as heat sealing layer or thermo-compression bonding layer.Below, as the printing stack membrane preferred scheme is described.
The printing stack membrane
Based on laminated film of the present invention, when using as the printing stack membrane, as the propylene resin film, preferably be that random copolymer resin is coextruded into 2 layers and become sheet with propylene resin and the crystallinity propylene that is described in detail above, and the biaxial stretch-formed polypropylene film that on direction in length and breadth, stretches.As propylene resin,, should be that 0.1～50g/10 minute, fusing point are 150～180 ℃ suitable selections of Noblen, the random polymers of propylene alpha-olefin from MFR from the viewpoint of gloss, rigidity.Preferably MFR is that 1～10g/10 minute, fusing point are 155～170 ℃ Noblens.
Crystallinity propylene at biaxial stretch-formed polypropylene film is on the random copolymer resin aspect, does not accompany tackifier coating agent ground vinylite is melt extruded lamination, and be used to print stack membrane.Because good with the caking property of the printing surface of tablet, is desirable so carry out the oxidation processes of sided corona treatment, ozone treatment etc. on the vinylite aspect for the printing stack membrane that obtains like this.Particularly sided corona treatment is the easiest and produce effect.
The printing stack membrane that obtains like this, thermo-compression bonding makes the printing laminated product on printing paper.But serviceability temperature is 60～120 ℃ a warm-up mill, with the pressure of roller line pressure 5～100kg the thermo-compression bonding layer and the printing paper of printing stack membrane is carried out thermo-compression bonding.
Embodiment
Below, be described more specifically the present invention according to embodiment, but the present invention is not subjected to the restriction of these embodiment.
1. the evaluation method of film
(1) adhesion strength of vinylite layer and propylene resin rete
Shown value is the test film that laminated film is cut into width 15mm, length 100mm, behind hand strip length direction 50mm, with Shimadzu Seisakusho Ltd.'s cupping machine in 90 values of spending on the directions hot strength of having peeled off with 300mm/ minute draw speed.
2. print the evaluation method of laminated product
(1) gloss
Measure the glossiness (20 degree) of the Printing Department of printing laminated product according to JIS-K7150.In determinator, use the UGV-5DP (trade name) of ス ガ testing machine society system.
(2) morphotropism
With visualization morphotropism (adherence of printing paper and lamination binding resin), estimate with following metewand.
The deformation state evaluation of outward appearance
There is not remaining air fully, print color distinctness zero
Air is with striation and the remaining △ of spot on print color
Air is banded remaining on print color, and print color is not distinct *
(3) adhesion strength of printing stack membrane and printing paper
Shown value is the test film that the printing laminated product is cut into width 25mm, length 100mm, behind the hand strip length direction 50mm, the value of the hot strength of on 180 degree directions, having peeled off with Shimadzu Seisakusho Ltd.'s cupping machine with 300mm/ minute draw speed.
(4) tunnel-effect
On the non-binding face of printing paper of printing laminated product,, be placed on 23 ℃ of temperature, under the atmosphere of humidity 50%, observe the variation of the lamination face after 24 hours, estimate with following evaluation criterion with the microsyringe light oil 100 μ l that drip.
The tunnel-effect evaluation
◎ adhesion strength, outward appearance are no problem fully
Zero adhesion strength reduces a little, but outward appearance does not change (anti-usage degree)
△ takes place granular a little
* tunnel-effect obviously takes place
3. resin is used in test
PP-1: crystallinity Noblen ノ バ テ Star Network PP FL6CK (Japanese Port リ ケ system (strain) system)
PP-2: the propylene and ethylene random copolymer resin is with following method manufacturing.
The preparation of co-catalyst
In the detachable flask, add the distilled water 1130g that wherein contains 96% sulfuric acid (750g), then, add montmorillonite family silicate (the system ベ of marshy land chemistry society Application Network レ イ SL down at 30 ℃; Average grain diameter 27 μ m, 300g).These slurries were warmed up to 90 ℃ with 1.0 ℃/minute through 1 hour, reacted 300 minutes down at 90 ℃.This reacting slurry with 1 hour cool to room temperature, is washed pH3 with distilled water.The solid that obtains is flowed down at 130 ℃ down after predrying 2 days at nitrogen, remove the above oversize grain of 53 μ m and 53 μ m, and then, obtain montmorillonite 2 08.3g again in 200 ℃ of following drying under reduced pressure 2 hours.
In the detachable flask, after adding distilled water 521g makes solution in lithium sulfate 1 hydrate (211g), add above-mentioned montmorillonite.After these slurries are at room temperature stirred 240 minutes, filter with the Bu Shi filter and to obtain the clay filter cake.In this clay filter cake, add distilled water 3000g and make slurries, stir after 10 minutes, refilter and obtain filter cake.To operate and repeat (pH of final filtrate is 6) 3 times, the filter cake that obtains is flowed down at 130 ℃ down after predrying 1 day at nitrogen, and remove the above oversize grain of 53 μ m, and then drying under reduced pressure 2 hours again under 200 ℃ obtains chemical treatment montmorillonite 80g thus.
The modulation of solid catalyst component
In 3 mouthfuls of flasks (1 liter of volume), add by the above-mentioned chemical treatment montmorillonite 2 0g that obtains, add heptane (73ml) and make slurries, adding tri-n-octylaluminium (the n-heptane solution 126.3ml of 50mmol: concentration 145.2mg/ml) therein stirred after 1 hour, with heptane wash to 1/100, add heptane, so that total measurement (volume) becomes 200ml.
In other flask (volume 200ml), [(r-) dichloro [1 in adding in the heptane (87ml) that contains 3 weight % toluene, two { 2-methyl-4-(4-the chlorphenyl)-4H-yl } zirconiums of 1 '-dimethylated methylene silylation] (0.3mmol) make slurries after, add triisobutyl aluminium (the n-heptane solution 2.13ml of 1.5mmol: concentration 140mg/ml) and at room temperature stir and reacted in 60 minutes.This solution is joined in above-mentioned (added reacted with tri-n-octylaluminium chemical treatment montmorillonite) 1 liter of flask, at room temperature stirred 60 minutes.Then, append heptane 213ml, these slurries are joined in 1 liter of autoclave.
After making the internal temperature of autoclave reach 40 ℃, propylene is kept 40 ℃ and carried out prepolymerization 2 hours with 10kg/ hour speed.Then, it is reinforced to stop propylene, keeps 40 ℃ constantly to carry out the polymerization of 1 hour residue internal temperature.Remove the supernatant liquor of the catalyst slurry that obtains with decantation, this solid drying under reduced pressure was obtained dry pre-polymerized catalyst 72.9g in 3 hours.
Polymerization
In the reactor of 400 liters of internal volumes, supply with the hexane dilute solution of aqueous propylene, ethene, hydrogen and triisobutyl aluminium continuously, interior temperature is remained on 60 ℃.The quantity delivered of propylene is 123kg/ hour, and the quantity delivered of ethene is 3.5kg/ hour, and the quantity delivered of hydrogen is 0.21g/ hour, and the quantity delivered of triisobutyl aluminium is 25g/ hour.(east combustion society system: modulation pre-polymerized catalyst ホ ワ イ ト レ Star Network ス 335) makes concentration become 20 weight %, with charging in 3.0g/ hour at atoleine.Its result obtains 19g/ hour propylene and ethylene random copolymer.
PP-3: the propylene and ethylene random copolymer is in order to the below manufactured.
Preparation of catalysts
In the glass reactor that has paddle of 0.5 liter of internal volume, add the system SiO of WITCO society
2Carry and hold MAO 2.4g (20.7mmol-Al), add normal heptane 50ml, add use dilution with toluene in advance two (2-methyl benzo indenyl) the zirconium solution 20.0ml (0.0637mmol) of dichloro (r)-dimethylated methylene silylation, then, add triisobutyl aluminium n-heptane solution 4.14ml (3.03mmol).After at room temperature reacting 2 hours, propylene is flowed into, carry out prepolymerization.
Polymerization
Behind the autoclave with the stirring-type of long-pending 200 liters of the abundant permutations of propylene, add triethyl aluminum 3g, the liquefied propylene 45kg, the ethene 0.77kg that have diluted with normal heptane, interior temperature is remained on 30 ℃.Then, add solid catalyst (as the weight of the having removed the prepolymerization polymer) 1.0g synthesized in advance.Then, be warmed up to 65 ℃ of beginning polymerizations, kept its temperature 3 hours.At this, add ethanol 100ml, stop reaction.Remove residual gas, obtain the propylene and ethylene random copolymer.
PP-4: the propylene and ethylene random copolymer resin is in order to the below manufactured.
Polymerization
Behind the autoclave with the stirring-type of long-pending 200 liters of the abundant permutations of propylene, add 60 liters of the normal heptanes made with extra care, under the propylene atmosphere, adding diethylaluminum chloride 45g, the red ソ Le ベ of ball-system titanium trichloride catalyst 16g of society under 55 ℃.And then, when keeping the gas phase hydrogen concentration 5.5 capacity % of portion, under 55 ℃ the temperature with the charging rate charging of propylene 5.8kg/ hour and ethene 0.36kg/ hour after 4 hours, and then continue polymerization 1 hour.Then, filter product and carry out drying, obtain the propylene and ethylene random copolymer.
PP-5: propylene and ethylene random copolymer resin ノ バ テ Star Network PPEG7F (Japanese Port リ ケ system (strain) system)
The rerum natura of above-mentioned PP-1～PP-5 is shown in Table 1.
Table 1
| Be total to monomer (content) (weight %) | ???Tm ??(℃) | MFR (g/10 branch) | ??Mw/Mn | ???ΔHm130 ????(J/g) | ????ΔHm ????(J/g) | ???ΔHm130/ΔHm | Polymerization catalyst | ||
| PP-1 | Homopolymers | ??- | 161.5 | ????2.4 | ????4.2 | ????7 | ????102.9 | ????0.07 | Mg load Ti system |
| PP-2 | Random copolymer | Ethene (3.8) | 125.2 | ????9.4 | ????2.7 | ????5.9.8 | ????60.4 | ????0.99 | Aromatic ring alkene metal derivative system |
| PP-3 | Random copolymer | Ethene (1.4) | 137.0 | ????6.1 | ????2.7 | ????45.8 | ????73.9 | ????0.62 | Aromatic ring alkene metal derivative system |
| PP-4 | Random copolymer | Ethene (5.2) | 136.0 | ????5.1 | ????3.7 | ????48.5 | ????77 | ????0.63 | TiCl 3System |
| PP-5 | Random copolymer | Ethene (3.3) | 143.0 | ????1.3 | ????6.2 | ????28.4 | ????81 | ????0.35 | Mg load Ti system |
Below, describe for embodiment, the used vinylite of comparative example.
LLDPE-1: at ethene 1-hexene copolymer resin M FR:30g/10 minute, density: 0.880g/cm
3, among the Mw/Mn:2.0, temperature rising elution fractionation (TREF), 80 ℃ elution amount: 100 weight % (Japanese Port リ ケ system (strain) system カ ネ-Le KJ640 (trade name)) aromatic ring alkene metal derivative based material
LLDPE-2: ethene 1-hexene copolymer resin M FR:11g/10 minute, density: 0.920g/cm
3, among the Mw/Mn:2.4, temperature rising elution fractionation (TREF), 80 ℃ elution amount: 87 weight % (Japanese Port リ チ system (strain) system カ ネ one Le KC581 (trade name)) aromatic ring alkene metal derivative based material
LDPE: high-pressure process low density polyethylene (LDPE) MFR:14g/10 minute, density: 0.919g/cm
3(Japanese Port リ ケ system (strain) system ノ バ Star Network LDLC701 (trade name))
4. the manufacturing of propylene resin film
(1)OPP-1
PP-1 is joined in the extruder, extrude the oriented film of total thickness 15 μ m from T pattern head, use the chill roll chilling, obtain the sheet of thickness 0.6mm thus, this sheet is stretched 5 times at longitudinal direction under 110 ℃ with the biaxial stretch-formed one by one device of tentering formula, then be preheating in stretching furnace after 160 ℃ under 158 ℃ and stretch at the stretching ratio of transverse direction with 9 times, 5% laxly carries out heat setting down under 158 ℃, and the individual layer biaxial stretch-formed polypropylene that obtains film gross thickness 15 μ m is film (OPP-1).
(2)OPP-2
In PP-2 powder 100 weight portions, cooperate the Ciba-Geigy society of the system イ of Ciba-Geigy (チ バ ガ イ キ one) society Le ガ ノ Star Network ス 1010,0.1 weight portion of 0.1 weight portion to make the calcium stearate of イ Le ガ Off オ ス 168,0.05 weight portion as antioxidant, after in the hot mixer in Hull (ヘ Le シ Application キ ミ キ サ one), stirring, in extruder, melt extrude, granulation, obtain the superficial layer resin combination.
The PP-1 that will use as the intermediate layer and join respectively in 2 extruders with resin combination as the above-mentioned superficial layer that superficial layer is used, go out from T pattern coextrusion head, skin depth when making 2 layers the oriented film of gross thickness 15 μ m becomes 2 μ m, chilling on chill roll, obtain the sheet of thickness 0.6mm thus, with this sheet with tentering formula one by one the twin shaft tenter device under 110 ℃, stretch 5 times at longitudinal direction, then in tentering formula stove, be preheating to after 160 ℃ and under 158 ℃, stretch at the stretching ratio of transverse direction with 9 times, 5% carries out heat setting under lax following 158 ℃, obtains film gross thickness 15 μ m, 2 kinds of 2 layers of biaxial stretch-formed polypropylenes of surface layer thickness 2 μ m are film (OPP-2).
(3)OPP-3
Except using the PP-3 powder as the raw material PP of superficial layer with resin combination, to operate in the same manner with the manufacturing of OPP-2,2 kinds of 2 layers of biaxial stretch-formed polypropylenes that obtain film gross thickness 15 μ m, surface layer thickness 2 μ m are film (OPP-3).
(4)OPP-4
Except using the PP-4 powder as the raw material PP of superficial layer with resin combination, to operate in the same manner with the manufacturing of OPP-2,2 kinds of 2 layers of biaxial stretch-formed polypropylenes that obtain film gross thickness 15m, surface layer thickness 2m are film (OPP-4).
(5)OPP-5
The PP-1 that will use as the intermediate layer and join respectively in 2 extruders as the PP-5 that superficial layer is used, go out from T pattern coextrusion head, skin depth when making 2 layers the oriented film of gross thickness 15 μ m becomes 2 μ m, chilling on chill roll, obtain the sheet of thickness 0.6mm, this sheet is stretched 5 times at longitudinal direction under 110 ℃ with the biaxial stretch-formed one by one device of tentering formula, then in tentering formula stove, be preheating to after 160 ℃ and under 158 ℃, stretch at the stretching ratio of transverse direction with 9 times, 5% is lax and carry out heat setting under 158 ℃, obtains film gross thickness 15 μ m, 2 kinds of 2 layers of biaxial stretch-formed polypropylenes of surface layer thickness 2 μ m are film (OPP-5).
(6)OPP-6
In PP-2 powder 100 weight portions, cooperate the calcium stearate of 0.1 weight portion as the system イ of Ciba-Geigy society Le ガ Off オ ス 168,0.05 weight portion of the system イ of Ciba-Geigy society Le ガ ノ Star Network ス 1010,0.1 weight portion of antioxidant, after in the hot mixer in Hull, stirring, in extruder, melt extrude, granulation, obtain resin combination.
Above-mentioned resin combination is joined in the extruder, go out from T pattern coextrusion head, chilling on chill roll, obtain the sheet of thickness 0.6mm thus, this sheet is stretched 5 times at longitudinal direction under 110 ℃ with the biaxial stretch-formed one by one device of tentering formula, then be preheating in tentering formula stove after 160 ℃ under 158 ℃ and stretch at the stretching ratio of transverse direction with 9 times, 5% is lax and carry out heat setting under 158 ℃, and the individual layer biaxial stretch-formed polypropylene that obtains film gross thickness 15 μ m is film (OPP-6).
Embodiment 1
(1) polyethylene mixture with the LDPE of the LLDPE-1 of 90 weight % and 10 weight % is encased in the extruder of bore 90mm, from being installed in T pattern head on this extruder, melt extrude into the membranoid substance of width 500mm, wall thickness 15 μ m 250 ℃ of resin temperatures.
(2) then, send OPP-2, on the surperficial aspect of OPP-2, melt extrude from T pattern head film shape ground from the unloading part of the base material of extruding laminated device, with the surface by coarse manufactured chill roll and the compressing rubber roll laminating lamination that bonds.And then at lamination the surface of binding resin layer of film carry out 20w minute/m
2Corona discharge Treatment, obtain laminated film.
(3) then, with the laminated film sided corona treatment face that obtains and hectographic printing art paper with 70,80,100 ℃ of roll temperatures, line pressure 55.6kg, speed 30m/ minute pressure cementing machine carries out thermo-compression bonding, obtains printing laminated product.
(4) with said method carry out for laminated film, printing paper add hot adhesion the evaluation of goods.The results are shown in table 2, the table 3.
Embodiment 2
(1) polyethylene mixture of the LDPE of LLDPE-1 that the intermediate layer of 80 weight % is used and 20 weight %, LLDPE-1 that superficial layer is used are respectively charged in 2 extruders of bore 65mm, from being installed in T pattern head on the extruder 250 ℃ of resin temperatures, with 2 layers of film that melt extrudes width 500mm, wall thickness 7 μ m and 8 μ m.
(2) then, send OPP-2 from the unloading part of the base material of extruding laminated device, in order on the surperficial aspect of OPP-2, to fit from T pattern head, use the surface to be roughened the chill roll and the compressing rubber roll laminating bonding lamination of processing with 2 layers of intermediate layer that melt extrudes into the film shape.And then at lamination the superficial layer surface of binding resin of film carry out 20w minute/m
2Corona discharge Treatment, obtain laminated film.
(3) following and embodiment 1 carries out in the same manner.The results are shown in table 2, the table 3.
Embodiment 3
Except in embodiment 2 (1), the fusion coextrusion resin temperature of polyethylene mixture is made outside 220 ℃, carry out in the same manner with embodiment 2.The results are shown in table 2, the table 3.
Embodiment 4
Except in embodiment 2 (2), OPP-2 is become outside the OPP-3, carry out in the same manner with embodiment 2.The results are shown in table 2, the table 3.
Comparative example 1
Except in embodiment 1 (2), OPP-2 is become outside the OPP-1, carry out in the same manner with embodiment 1.The results are shown in table 2, the table 3.Polyethylene layer and biaxial stretch-formed polypropylene are the remarkable deterioration of the adhesion strength of thin layer, and the gloss of printing laminated product, morphotropism, all insufficient with adhesion strength, the tunnel-effect of printing paper can not show the adaptability of printing lamination.
Comparative example 2
Except in embodiment 2 (2), OPP-2 is become outside the OPP-1, carry out in the same manner with embodiment 1.The results are shown in table 2, the table 3.The caking property of the biaxial stretch-formed polypropylene mesentery layer of polyethylene layer is poor significantly, and the gloss of printing laminated product, morphotropism, all insufficient with adhesion strength, the tunnel-effect of printing paper can not show the adaptability of printing lamination.
Comparative example 3
(1) with the T pattern head of LLDPE-2 from the extruder that is installed in bore 90mm 250 ℃ of resin temperatures, melt extrude the tympan of width 500mm, wall thickness 15 μ m.
(2) then, send OPP-2, on the surperficial aspect of OPP-2, melt extrude, with the chill roll of rough surface processing and the compressing rubber roll laminating lamination that bonds from T pattern head film shape ground from the unloading part of the base material of extruding laminated device.And then at lamination the surface of binding resin layer of film carry out 20w minute/m
2Corona discharge Treatment, obtain laminated film.
(3) below, carry out in the same manner with embodiment 1.The results are shown in table 2, the table 3.Polyethylene layer and biaxial stretch-formed polypropylene are that the adhesion strength of thin layer is abundant, but print gloss, the morphotropism, all poor significantly with adhesion strength, the tunnel-effect of printing paper of laminated product, can not show the adaptability of printing lamination.
Comparative example 4
(1) mixture of the LDPE of LLDPE-1 that the intermediate layer of 80 weight % is used and 20 weight %, LLDPE-1 that superficial layer is used respectively the T pattern head from 2 extruders that are installed in bore 65mm 250 ℃ of resin temperatures, with 2 layers of film that melt extrudes into width 500mm, wall thickness 7 μ m and 8 μ m.
(2) then, send OPP-5 from the unloading part of the base material of extruding laminated device, in order to fit from T pattern head with 2 layers of intermediate layer that melt extrudes into the film shape, with the chill roll and the compressing rubber roll laminating bonding lamination of rough surface processing.And then at lamination the superficial layer surface of binding resin of film on carry out 20w minute/m
2Corona discharge Treatment, obtain laminated film.
(3) following and embodiment 1 carries out in the same manner.The results are shown in table 2, the table 3.Polyethylene layer and biaxial stretch-formed polypropylene are that the adhesion strength of thin layer is insufficient a little, and the gloss of printing laminated product, morphotropism, all insufficient with adhesion strength, the tunnel-effect of printing paper can not show the adaptability of printing lamination.
Comparative example 5
Except with among the embodiment 2 (2), OPP-2 replaces to outside the OPP-4, and other and embodiment 2 operate in the same manner.It the results are shown in table 2, table 3.
Embodiment 5
Except with among the embodiment 1 (2), OPP-2 replaces to outside the OPP-6, and other and embodiment 1 operate in the same manner.It the results are shown in table 2, table 3.
Embodiment 6
Except with among the embodiment 2 (2), OPP-2 replaces to outside the OPP-6, and other and embodiment 2 operate in the same manner.It the results are shown in table 2, table 3.
Table 2
| The propylene resin film | Vinylite | Stack temperature (℃) | Adhesion strength *??(g/15mm) | ||
| Intermediate layer (mixed weight ratio) | Superficial layer | ||||
| Embodiment 1 | ????OPP-2 | ??LLDPE-1(90)+LDPE(10) | ??- | ????250 | ????170 |
| Embodiment 2 | ????OPP-2 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????250 | ????170 |
| Embodiment 3 | ????OPP-2 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????220 | ????150 |
| Embodiment 4 | ????OPP-3 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????250 | ????140 |
| Comparative example 1 | ????OPP-1 | ??LLDPE-1(90)+LDPE(10) | ??- | ????250 | ????10 |
| Comparative example 2 | ????OPP-1 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????250 | ????10 |
| Comparative example 3 | ????OPP-2 | ??LLDPE-2(100) | ??- | ????250 | ????100 |
| Comparative example 4 | ????OPP-5 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????250 | ????50 |
| Comparative example 5 | ????OPP-4 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????250 | ????120 |
| Embodiment 5 | ????OPP-6 | ??LLDPE-1(90)+LDPE(10) | ??- | ????250 | ????170 |
| Embodiment 6 | ????OPP-6 | ??LLDPE-1(80)+LDPE(20) | ??LLDPE-1(100) | ????250 | ????170 |
*: the adhesion strength of propylene resin film and vinylite
Table 3
| Gloss (%) | Morphotropism | Follow intensity **(g/25mm) | Tunnel-effect | |||||||||
| Roll temperature (℃) | Roll temperature (℃) | Roll temperature (℃) | Roll temperature (℃) | |||||||||
| ????70 | ????80 | ????100 | ????70 | ????80 | ???100 | ????70 | ????80 | ????100 | ????70 | ????80 | ????100 | |
| Embodiment 1 | ????75 | ????85 | ????90 | ????× | ????△ | ????○ | ????150 | ????350 | ????670 | ????△ | ????○ | ????◎ |
| Embodiment 2 | ????90 | ????92 | ????96 | ????○ | ????○ | ????○ | ????760 | ????1020 | ????1150 | ????◎ | ????◎ | ????◎ |
| Embodiment 3 | ????90 | ????92 | ????96 | ????○ | ????○ | ????○ | ????760 | ????1010 | ????1130 | ????◎ | ????◎ | ????◎ |
| Embodiment 4 | ????88 | ????90 | ????96 | ????○ | ????○ | ????○ | ????720 | ????990 | ????1110 | ????◎ | ????◎ | ????◎ |
| Comparative example 1 | ????50 | ????65 | ????80 | ????× | ????× | ????△ | ????50 | ????150 | ????200 | ????× | ????× | ????△ |
| Comparative example 2 | ????55 | ????70 | ????82 | ????× | ????× | ????△ | ????50 | ????170 | ????240 | ????× | ????× | ????△ |
| Comparative example 3 | ????50 | ????60 | ????78 | ????× | ????× | ????× | ????10 | ????50 | ????180 | ????× | ????× | ????× |
| Comparative example 4 | ????65 | ????70 | ????85 | ????× | ????× | ????○ | ????100 | ????220 | ????380 | ????× | ????△ | ????○ |
| Comparative example 5 | ????85 | ????88 | ????93 | ????○ | ????○ | ????○ | ????680 | ????840 | ????1080 | ????○ | ????◎ | ????◎ |
| Embodiment 5 | ????73 | ????84 | ????90 | ????× | ????△ | ????○ | ????160 | ????370 | ????690 | ????△ | ????○ | ????◎ |
| Embodiment 6 | ????91 | ????94 | ????96 | ????○ | ????○ | ????○ | ????750 | ????1040 | ????1140 | ????◎ | ????◎ | ????◎ |
The adhesion strength of resin molding and printing paper
Industrial applicibility
Be on the propylene resin film that forms of random copolymer resin by specific crystallinity propylene, do not accompany tackifier coating agent ground with the laminated film that melt extrudes the vinylite of the specific straight chain shape of lay-up method lamination ethyleneα-olefincopolymer as principal component and obtain, the cohesive force of the interlayer of propylene resin rete and vinylite layer is strong. Therefore, do not need the tackifier coating agent, the solvent that can save when using the tackifier coating agent is removed, retracting device etc., thus can avoid impact on operating environment, the danger of breaking out of fire. In addition, with the printing laminated product of printing paper thermo-compression bonding because strong with the cohesive force of printing paper, so can obtain the good goods of outward appearance. In addition, lamination can be printed at low temperatures with block letter, thereby the variable color of printing-ink of goods and curling can be prevented.
Claims (7)
1. laminated film, it is characterized in that, this laminated film is by on propylene resin film surface, do not accompany tackifier coating agent ground and do not melt extrude that the lamination vinylite constitutes, said propylene resin film is that crystallinity propylene below 140 ℃ and 140 ℃ is that random copolymer resin forms by using aromatic ring alkene metal derivative Preparation of Catalyst, melting hump temperature, and said vinylite is that the alpha-olefin copolymer with ethene and carbon number 3～20 obtains, density is 0.870～0.910g/cm
3, MFR is that 1～100g/10 minute straight chain shape ethylene is as principal component.
2. laminated film according to claim 1, wherein the crystallinity propylene is a random copolymer resin, to 130 ℃ fusing heat (Δ Hm
130) with respect to ratio (the Δ Hm of total fusing heat (Δ Hm)
130/ Δ Hm) be more than 0.5 and 0.5.
3. laminated film according to claim 1 and 2, therein ethylene are that resin is a polyethylene mixture, and the alpha-olefin copolymer by ethene and carbon number 3～20 that this mixture contains 60～99 weight % closes and the density that obtains is 0.870～0.910g/cm
3, MFR is that the MFR of 1～100g/10 minute straight chain shape ethylene and 1～40 weight % is 1～50g/10 minute a high-pressure process low density polyethylene (LDPE).
4. according to any one described laminated film of claim 1～3, it is characterized in that, straight chain shape ethylene is 80 ℃ a elution amount measuring by temperature rising elution fractionation (TREF) with respect to the copolymer total amount is 90 weight % and more than the 90 weight %.
5. according to any one described laminated film of claim 1～4, wherein, straight chain shape ethylene is to use aromatic ring alkene metal derivative catalyst to make.
6. according to any one described laminated film of claim 1～5, it is characterized in that the stack temperature that melt extrudes of vinylite is 150～300 ℃.
7. one kind is printed laminated product, and it is that the vinylite face of any one described laminated film in the claim 1～6 and printing paper are carried out the thermo-compression bonding formation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP293386/2001 | 2001-09-26 | ||
| JP2001293386 | 2001-09-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1558826A true CN1558826A (en) | 2004-12-29 |
| CN1301190C CN1301190C (en) | 2007-02-21 |
Family
ID=19115185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028189795A Expired - Lifetime CN1301190C (en) | 2001-09-26 | 2002-09-25 | Laminated film |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7341794B2 (en) |
| KR (1) | KR100661248B1 (en) |
| CN (1) | CN1301190C (en) |
| WO (1) | WO2003026890A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070054091A1 (en) * | 2005-09-02 | 2007-03-08 | Yupo Corporation | Label for in-mold molding and resin container decorated with the same |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2983814B2 (en) | 1993-10-21 | 1999-11-29 | 三菱化学株式会社 | Printed laminate products |
| US5962092A (en) * | 1994-03-28 | 1999-10-05 | Cryovac, Inc. | Oxygen-permeable multilayer film containing antifog agent and package made therefrom |
| US5491019A (en) * | 1994-03-28 | 1996-02-13 | W. R. Grace & Co.-Conn. | Oxygen-permeable multilayer film |
| SG38896A1 (en) * | 1994-12-22 | 1997-04-17 | Sumitomo Chemical Co | Polypropylene composition and laminated and oriented film therefrom |
| CA2228551A1 (en) * | 1995-09-18 | 1997-03-27 | Exxon Chemical Patents, Inc. | High barrier polypropylene compositions and their use in packaging applications |
| JPH10180964A (en) | 1996-10-24 | 1998-07-07 | Mitsubishi Chem Corp | Biaxially oriented multilayer film |
| JP3098731B2 (en) | 1997-08-27 | 2000-10-16 | 三菱化学株式会社 | Laminated film |
| JPH11342568A (en) * | 1998-05-29 | 1999-12-14 | Mitsubishi Chemical Corp | Stretch packaging film |
| JP4240634B2 (en) | 1999-02-12 | 2009-03-18 | 日本ポリプロ株式会社 | Biaxially stretched multilayer film |
| JP4030659B2 (en) | 1998-07-01 | 2008-01-09 | 日本ポリプロ株式会社 | Biaxially stretched polypropylene film |
| JP2000062117A (en) | 1998-08-25 | 2000-02-29 | Japan Polychem Corp | Laminated film |
| JP4308944B2 (en) * | 1998-09-17 | 2009-08-05 | 出光興産株式会社 | Polypropylene multilayer film |
| JP3876619B2 (en) * | 1999-12-01 | 2007-02-07 | 住友化学株式会社 | Packaging film |
| JP2001260291A (en) * | 2000-03-21 | 2001-09-25 | Idemitsu Petrochem Co Ltd | Polypropylene multilayer film |
-
2002
- 2002-09-25 CN CNB028189795A patent/CN1301190C/en not_active Expired - Lifetime
- 2002-09-25 US US10/490,109 patent/US7341794B2/en not_active Expired - Lifetime
- 2002-09-25 KR KR1020047004488A patent/KR100661248B1/en not_active IP Right Cessation
- 2002-09-25 WO PCT/JP2002/009837 patent/WO2003026890A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN1301190C (en) | 2007-02-21 |
| US20040216846A1 (en) | 2004-11-04 |
| WO2003026890A1 (en) | 2003-04-03 |
| US7341794B2 (en) | 2008-03-11 |
| KR20040070333A (en) | 2004-08-07 |
| KR100661248B1 (en) | 2006-12-27 |
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